Release surfaces, particularly for use in nanoimprint lithography

ABSTRACT

The addition of thin coatings (less than and approaching monomolecular coatings) of persistent release materials comprising preferred compounds of the formula:  
     RELEASE-M(X) n -1  
     RELEASE-M(X) n-m-1  Q m ,  
     or  
     RELEASE-M(OR) n -1 -, wherein  
     RELEASE is a molecular chain of from 4 to 20 atoms in length, preferably from 6 to 16 atoms in length, which molecule has either polar or non-polar properties;  
     M is a metal atom, semiconductor atom, or semimetal atom;  
     X is halogen or cyano, especially Cl, F, or Br;  
     Q is hydrogen or alkyl group;  
     m is the number of Q groups;  
     R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1 to 4 carbon atoms; and;  
     n is the valence −1 of M,  
     and n-m-1 is at least 1  
     provides good release properties. The coated substrates are particularly good for a lithographic method and apparatus for creating ultra-fine (sub-25 nm) patterns in a thin film coated on a substrate is provided, in which a mold having at least one protruding feature is pressed into a thin film carried on a substrate. The protruding feature in the mold creates a recess of the thin film. The mold is removed from the film. The thin film then is processed such that the thin film in the recess is removed exposing the underlying substrate. Thus, the patterns in the mold is replaced in the thin film, completing the lithography. The patterns in the thin film will be, in subsequent processes, reproduced in the substrate or in another material which is added onto the substrate.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to release surfaces, particularlyrelease surfaces with fine features to be replicated, and to lithographywhich may be used to produce integrated circuits and microdevices. Morespecifically, the present invention relates to a process of using animproved mold or microreplication surface that creates patterns withultra fine features in a thin film carried on a surface of a substrate.

[0003] 2. Background of the Art

[0004] In many different areas of technology and commercial utility, itis highly desirable that surface be provided with non-stickfunctionality. The wide range of utility for this type of technologyranges from antistain treatments for fabrics and surfaces (e.g.,countertops, stove tops, and the like), to utensils (e.g., cooking orlaboratory utensils and surfaces), release surfaces for imagingtechnology (e.g., image transfer surfaces, temporary carriers), and moldrelease surfaces. Antistick functionality has clear lubricatingimplications where the antistick function can be provided in asubstantive or retentive manner onto a substrate.

[0005] In the fabrication of semiconductor integrated electricalcircuits, integrated optical, magnetic, mechanical circuits andmicrodevices, and the like, one of the key processing methods islithography and especially photolithography. Lithography can be used,along with its traditional resist imaging in the formation of printingplates and resist images, to create a pattern in a thin film carried ona substrate so that, in subsequent process steps, the pattern can bereplicated in the substrate or in another material which is added ontothe substrate. The thin film which accepts a pattern or image during thelithographic process is often referred to as resist. The resist may beeither a positive resist or a negative resist, depending on itsoperation of formation. For example, a positive photoresist becomes moresoluble in a solvent where irradiated and a negative resist becomes moreinsoluble where irradiated. A typical lithographic process forintegrated circuit fabrication involves exposing or irradiating aphotoresist composition or film with a beam of radiation or particles,including light, energetic particles (which may be electrons), photons,or ions, by either passing a flood beam through a mask or scanning afocused beam. The radiation or particle beam changes the chemicalstructure of the exposed area of the film, so that when washed orimmersed in a developer or washed with a developer, either the exposedarea or the unexposed area of the resist will be removed to recreate thepatterns or its obverse of the mask or the scanning. The lithographyresolution is limited by the wavelength of the particles and theresolution of the beam, the particle scattering in the resist and thesubstrate, and the properties of the resist.

[0006] There is an ongoing need in art of lithography to produceprogressively smaller pattern sizes while maintaining cost efficiency inthe process. There is a great need to develop low-cost technologies formass producing sub-50 nm structures since such a technology could havean enormous impact in many areas of engineering and science. Not onlywill the future of semiconductor integrated circuits be affected, butalso the commercialization of many innovative electrical, optical,magnetic, mechanical microdevices that are far superior to currentdevices will rely on the possibility of such technology. Additionallyoptical materials, including reflective coatings and reflective sheeting(as may be used for security purposes or for signage) can usemicroreplication techniques according to lithographic technology.

[0007] Numerous technologies have been developed to service these needs,but they all suffer serious drawbacks and none of them can mass producesub-50 nm lithography at a low cost. Electron beam lithography hasdemonstrated 10 nm lithography resolution. A. N. Broers, J. M. Harper,and W. W. Molzen, Appl. Phys. Lett. 33, 392 (1978) and P. B. Fischer andS. Y. Chou, Appl. Phys. Lett. 62, 2989 (1993). However, using thesetechnologies for mass production of sub-50 nm structures seemseconomically impractical due to inherent low throughput in a serialprocessing tool. X-ray lithography, which can have a high throughput,has demonstrated 50 nm lithography resolution. K. Early, M. L.Schattenburg, and H. I. Smith, Microelectronic Engineering 11, 317(1990). But X-ray lithography tools are rather expensive and its abilityfor mass producing sub-50 nm structures is yet to be commerciallydemonstrated. Lithography based on scanning probes has produced sub-10nm structures in a very thin layer of materials. However, thepracticality of such lithography as a manufacturing tool is hard tojudge at this point.

[0008] Imprint technology using compressive molding of thermoplasticpolymers is a low cost mass manufacturing technology and has been aroundfor several decades. Features with sizes greater than 1 micrometers havebeen routinely imprinted in plastics. Compact disks which are based onimprinting of polycarbonate are one example of the commercial use ofthis technology. Other examples are imprinted polymethyl methacrylate(PMMA) structures with a feature size on the order to 10 micrometers formaking micromechanical parts. M. Harmening, W. Bacher, P. Bley, A.El-Kholi, H. Kalb, B. Kowanz, W. Menz, A. Michel, and J. Mohr,Proceedings IEEE Micro Electro Mechanical Systems, 202 (1992). Moldedpolyester micromechanical parts with feature dimensions of several tensof microns have also been used. H. Li and S. D. Senturia, Proceedings of1992 13th IEEE/CHMT International Electronic Manufacturing TechnologySymposium, 145 (1992). However, no one has recognized the use of imprinttechnology to provide 25 nm structures with high aspect ratios.Furthermore, the possibility of developing a lithographic method thatcombines imprint technology and other technologies to replace theconventional lithography used in semiconductor integrated circuitmanufacturing has never been raised.

SUMMARY OF THE INVENTION

[0009] The present invention relates to methods for changing theproperties of surfaces by bonding coatings of molecules to surfaces toform noncontinuous coatings of molecules bonded thereto. The inventionis particualrly advantageous for forming mold or microreplicationsurfaces having coatings of molecules bonded thereto, and to processesof molding and microreplication using these coatings and surfaces. Thecoatings may be referred to as noncontinuous coatings as the coatingmaterial does not have to bond cohesively with itself parallel to thesurface which is coated, but is bonded, molecule-by-molecule, to thesurface, such as grass protrudes, blade-by-blade, from the surface ofthe ground.

[0010] The present invention relates to a method for providing a surfacewith a treatment that can render the surface more effective in moldingor microreplication processes. A molecular moiety having releaseproperties towards other materials (e.g., fluorinated hydrocarbon chainsor polysiloxanes) and low chemical reactivity to moldable polymers isbonded to a mold or microreplication surface. The release properties ofthe molecular moiety having release properties allows for theenhancement of resolution on the molded article since the moldedmaterial is released from the minute features of the mold on a molecularlevel. More common polymeric coated release surfaces can fill theopenings or partially fill the openings of the mold. Merely smootherrelease surfaces expose the surface of the mold to abrasion and toreaction with the molding materials. The description of the coating asnon-continuous may be described as follows. A continuous coatingnormally is one that forms a film on the surface with no direct routefrom one side of the film to the other side of the film. As there is notrue film coating formed in the practice of the present invention, butrather individual molecules tend to be stacked up on the surface, thereis no continuous coating, even though there may be uniform propertiesover the surface. On a molecular level, the surface would appear as asurface having one moiety at one end of a relatively linear moleculebonded to the surface. The relatively linear molecule extends away fromthe surface, with the release properties provided by the ‘tail’ of themolecule that extends away from the surface. The relative concentrationof tails on the surface controls thehydrophilic/hydrophobic/polar/non-polar properties of the surface sothat it will enable ready release of the material provided by themolding or microreplication process. The release portion of the adheredmolecule will preferably have few reactive sites on the tail,particularly within the last one, two, three or four skeletal atoms inthe relatively linear chain (e.g., with a hydrocarbon-based chain, thealpha, beta, gamma, and delta atoms in the chain). Such moieties to beavoided particularly would include free hydrogen containing groups(e.g., acid groups, carboxylic acid groups or salts, sulfonic acidgroups or salts, amine groups, ethylenically unsaturated groups, and thelike).

[0011] The present invention also relates to a method and apparatus forperforming ultra-fine line lithography of the type used to produceintegrated circuits and microdevices. A layer of thin film is depositedupon a surface of a substrate. A mold having its mold surface treatedwith the release materials of the present invention and at least oneprotruding feature and a recess is pressed into the thin film, thereforethe thickness of the film under the protruding feature is thinner thanthe thickness of the film under the recess and a relief is formed in thethin film. The relief generally conforms to the shape of the feature onthe mold. After the mold is removed from the film, the thin film isprocessed such that the thinner portion of the film in the relief isremoved exposing the underlying substrate. Thus, the pattern in the moldis replicated in the thin film, completing the lithography. The patternsin the thin film will be, in subsequent processes, reproduced in thesubstrate or in another material that is added onto the substrate. Theuse of the release treatment on the mold surface enhances the resolutionof the image and can protect the mold so that it can be used more oftenwithout showing wear on fine features in the mold.

[0012] The invention described here is based on a fundamentallydifferent principle from conventional lithography. The process inventioncan eliminate many resolution limitations imposed in conventionallithography, such as wavelength limitation, backscattering of particlesin the resist and substrate, and optical interference. It has beendemonstrated the present invention can include a high throughput massproduction lithography method for generating sub-25 nm features.Furthermore, the present invention has the ability to mass producesub-10 nm features at a low cost. These capabilities of the presentinvention is unattainable with the prior art, and the use of theadherent release property coating improves the durability and theresolution of the process even further. The present process, however,has implications and utility for more macroscopic details in moldingsurfaces and would include features in the super-50 nm range, thesuper-100 nm range, and the super 200 nm range, as well as macroscopicdimensions in the visual range of features (e.g., 0.1 mm and greater).

BRIEF DESCRIPTION OF THE DRAWINGS

[0013]FIG. 1A is a cross sectional view showing a mold and substrate inaccordance with the present invention.

[0014]FIG. 1B is a cross sectional view of the mold and substrate ofFIG. 1A showing the mold pressed into a thin film carried on thesubstrate.

[0015]FIG. 1C is a cross sectional view of the substrate of FIG. 1Bfollowing compression of the mold into the thin film.

[0016]FIG. 1D is a cross sectional view of the substrate of FIG. 1Cshowing removal of compressed portions of the thin film to expose theunderlying substrate.

[0017]FIG. 5A is a cross sectional view of the substrate of FIG. 1Dfollowing deposition of a material.

[0018]FIG. 5B is a cross sectional view of the substrate of FIG. 5Afollowing selective removal of the material by a lift off process.

[0019]FIG. 8 is a cross sectional view of the substrate of FIG. 1Dfollowing subsequent processing.

[0020]FIG. 9 is a simplified block diagram of an apparatus in accordancewith one embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention relates to methods for changing theproperties of surfaces by bonding non-continuous coatings of moleculesthereto, to surfaces having non-continuous coatings of molecules bondedthereto, to mold or microreplication surfaces having non-continuouscoatings of molecules bonded thereto, and to processes of molding andmicroreplication using these coatings and surfaces.

[0022] This invention also relates to a method and apparatus for ahigh-resolution, high-throughput, low-cost lithography. Unlike currentmicrolithography, a preferred embodiment of the present inventionabandons usage of energetic light or particle beams. Photolithographymay also benefit from the practice of the present invention by the useof the reactive release layer bonded to the mold surface. In theembodiment of the invention which does not require the use ofphotolithography, the present invention is based on pressing a mold intoa thin film on a substrate to create a relief and, later removing thecompressed area of the film to expose the underlying substrate and toform a resist pattern on the substrate that replicates the obverse ofthe protruding pattern of the mold.

[0023] The present invention also has demonstrated the generation ofpatterns, such as holes, pillars, or trenches in a thin film on asubstrate, that have a minimum size of 25 nm, a depth over 100 nm, aside wall smoothness better than 3 nm, and corners with near perfect 90degrees angles. It was found that presently the size of imprintedfeatures is limited by the size of the mold being used; with a suitablemold, the present invention should create sub-10 nm structures with ahigh aspect ratio. Furthermore, using one embodiment of the presentinvention that including a material deposition and a lift-off process,100 nm wide metal lines of a 200 nm period and 25 nm diameter metal dotsof 125 nm period have been fabricated. The resist pattern created usingthe present invention also has been used as a mask to etchnanostructures (features having dimensions less than 1000 nm, preferablyless than 500 nm) into the substrate.

[0024] The present invention offers many unique advantages over theprior art. First, since it is based on a paradigm different from theprior art and it abandons the usage of an energetic particle beam suchas photons, electrons, and ions, the present invention eliminates manyfactors that limit the resolution of conventional lithographies, such aswave diffraction limits due to a finite wavelength, the limits due toscattering of particles in the resist and the substrate, andinterferences. Therefore the present invention offers a finerlithography resolution and much more uniform lithography over entiresubstrate than the prior art. Results show it can achieve sub-25 nmresolution. Second, the present invention can produce sub-25 nm featuresin parallel over a large area, leading to a high throughput. This seemsunachievable with the prior art. And thirdly, since no sophisticatedenergetic particle beam generator is involved, the present invention canachieve a sub-25 nm lithography over a large area at a cost much lowerthan the prior art. These advantages make the present invention superiorto the prior art and vital to future integrated circuit manufacturingand other areas of science and engineering where nanolithography isrequired.

[0025] The non-continuous coatings of molecules are formed from aspecific type of reactive compound. These compounds may be characterizedby the following structure:

RELEASE-M(X)_(n)

or

RELEASE-M(OR)_(n), wherein

[0026] RELEASE is a molecular chain of from 4 to 20 atoms in length,preferably from 6 to 16 atoms in length, which molecule has either polaror non-polar properties, depending upon the phobicity desired towards amolding agent;

[0027] M is an inorganic atom, especially a metal atom, semiconductoratom, or semimetal atom;

[0028] X is halogen or cyano, especially Cl, F, or Br;

[0029] R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1to 4 carbon atoms, most preferably hydrogen, methyl or ethyl; and;

[0030] (n) is the valence −1 of M, usually 1, 2 or 3 depending upon thenature of M.

[0031] The actual moiety bonded to the surface has one of the groupsbonded to the metal or semimetal atom removed during a reaction with themold surface and may have the structural formula:

RELEASE-M(X)_(n-1)

or

RELEASE-M(OR)_(n-1)-, wherein

[0032] RELEASE is a molecular chain of from 4 to 20 atoms in length,preferably from 6 to 16 atoms in length, which molecule has either polaror non-polar properties;

[0033] M is a metal or semimetal atom;

[0034] X is halogen or cyano, especially Cl, F, or Br;

[0035] R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1to 4 carbon atoms; and;

[0036] (n) is the valence −1 of M.

[0037] As noted above, the properties of RELEASE are determined in partby the nature of the molded material to be used with the surface or thenature of the properties desired on the surface. That is where thesurface is to be used in microreplication with a polar polymericmaterial, the RELEASE properties must be non-polar. Non-polar RELEASEgroups are preferably selected, for example, from non-polar molecularunits including especially siloxane units and highly fluorinated orfluorocarbon units. It is further preferred that these non-polarmolecular units are linear units of from 4 to 20 skeletal atoms in thelinear chain. Smaller chains might not form as continuous of releaseproperties as desired, and longer chains might mask features on thesurface to be replicated. By highly fluorinated is meant that at least ⅔of all substituents on the carbon are fluorinated units, with theremaining units comprising Cl or H. Preferably the terminal carbon isperfluorinated, more preferably the terminal carbon atom isperfluorinated and no hydrogen atoms are present on the three terminalcarbon atoms, and most preferably the chain is perfluorinated.

[0038] M is preferably a metal atom, semiconductor atom or semimetalatom such as for example, Si, Ti, Zr, Cr, Ge, and the like. Mostpreferably M is Si. In these cases, n would preferably be 3.

[0039] Examples of the compounds which can be used in the practice ofthe present invention comprise perfluorohexyl trichlorosilane,perfluorooctyl trichlorosilane, perfluorodecyl trichlorosilane,perfluorododecyl trichlorosilane, perfluorohexylpropyl trichlorosilane,perfluorodecyl trichlorotitanium, perfluorodecyl dichlorobromosilane,polydimethylsiloxane-trichlorosilane (with n preferably of about 4 to 20for the polydimethylsiloxane unit), perfluorodecyldichlorobromogermanium, perfluorodecyl dichlorobromochromium, and thelike.

[0040] The mold surfaces to be used may be any surface to which therelease providing molecules may bond. By selecting appropriate releaseproviding molecules, substantially any release surface may be used. Therelease surface may be metallic, semimetallic, metal oxides, metal andsemimetal carbides and nitrides, semimetallic oxide, polymeric,semiconductors, photocinductors, ceramic, glass, composite or the like,as is known in the molding and microreplication art. Particularly usefulsubstrates include, but are not limited to, silicon, silicon nitride,silicon carbide, silicon nitride, doped semiconductor blends,photoconductors (both organic and inorganic), and the like. The moldingprocess may include impression molding as generally described above,injection molding, powder molding, blow molding, casting or castmolding, vapor deposition molding, decomposition molding (wherematerials are decomposed to form new materials which deposit on thesurface), and the like. Uniformly shaped patterns or random patterns maybe manufactured, and the materials used in the molding composition mayharden, as previously noted, by cooling thermally softened materials,polymerizable materials, chemically reacting materials, vapor depositingmaterials, or the like. Preferred materials comprise semiconductor,dielectric, photoresponsive, thermally responsive, or electricallyresponsive substrates or surfaces, such as, but not limited to,inorganic oxides (or sulfides, halides, carbides, nitrides, etc.), rareearth oxides (or sulfides, halides, carbides, nitrides, etc.), inorganicor organic silicon compounds (e.g., silica oxides, sulfides, halides,carbides, nitrides, etc.) and their titanium, germanium, cadmium, zincand the like counterparts (e.g., titania, zinc oxide [particles orlayers], germanium oxide, cadmium sulfide) as continuous ordiscontinuous coatings or layers, as mixture, dispersions or blends, aslayered structures, and the like.

[0041] The release-coating forming materials of the present inventionmay be applied in coatings which form less than continuous monomolecularlayers of the release material. That is, the release material formscoatings comprising tails of the release moiety secured to the surfaceby reaction with the nominatively inorganic end of the molecule (e.g.,the silicon, titanium, germanium, end). The entire surface of thesubstrate is not necessarily coated, as the release molecules tend toprevent other molecules from aligning uniformly (at least uniformly in apattern) along the surface. There may be, and most likely always is,some spacing between the individual coating molecules on the surfacesince, as shown in FIG. 1A, the coating does not form as a continuouslayer parallel to the coated surface, but rather forms as extendedmolecules bonded at only one end to the surface, leaving the RELEASEgroup outwardly extending to provide the release (non-stick) properties.However, the release moiety tail of the compounds evidences an area oflubricity, so a uniform coating is not essential. Coating weights of therelease coating material may be used in surprisingly small amounts,considering their effectiveness. For example, coating weights of lessthan 0.001 mg/m² of surface area have provided significant releasecoating effects. Coating weights 0 f 0.001 to 100 or more mg/m² ofsurface area, from 0.005 to 5 mg/m² of surface area, and preferably from0.01 up to 1 to 5 mg/m² of surface area are generally useful.

[0042] FIGS. 1A-1D show steps in accordance with one embodiment. FIG. 1Ashows molding layer 10 having body 12 and molding layer 14. The releasecoating material Si-RELEASE is shown attached to said molding layer 10,although not proportionally. The Si-RELEASE compound is shown as singlemolecules bonded at the Si end, with the RELEASE tail extendingtherefrom to provide the release properties to the mold 14. The size ofthe release compound residues -Si-RELEASE is molecular as opposed to themacromolecular view of the molding surface 14 shown in the FIG. 1A. Theresidual groups which may be attached to the Si (e.g., unreacted H,cyano, or halogen) are not shown, merely for convenience in drawing theFigure. As can be seen from this less than literal representation, theRELEASE moities extend away from the molding surface 14. These RELEASE“tails” provide the release property and tend to be fairly durable andpersistent. Molding layer 14 is shown as including a plurality offeatures 16 having a desired shape. A release layer 17 is shown bondedto the surface of the features 16 on the molding layer 14. A substrate18 carries thin film layer 20. Thin film layer 20 is deposited throughany appropriate technique such as spin casting, slot die coating, slidecoating, curtain coating, solvent coating, gravure coating, screencoating, vapor deposition, sputtering and the like.

[0043]FIG. 1B shows a compressive molding step where mold 10 is pressedinto thin film layer 20 in the direction shown by arrow 22 formingcompressed regions 24. In the embodiment, shown in FIGS. 1A-1D, features16 are not pressed all of the way into thin film 20 and do not contactsubstrate 18. In some embodiments, top portions 24 a of film 20 maycontact depressed surfaces 16 a of mold 10. This causes top surfaces 24a to substantially conform to the shape of surfaces 16 a, for exampleflat. When contact occurs, this also can stop the mold move further intothe thin film 20, due to a sudden increase of contact area and hence adecrease of the compressive pressure when the compressive force isconstant. The release layer 17 of the present inventions improves therelease of the thin film layer 20 from the features 16 of the mold 10.

[0044]FIG. 1C is a cross sectional view showing thin film layer 20following removal of mold 10. Layer 20 includes a plurality of recessesformed at compressed regions 24 which generally conform to the shape offeatures 16 which is coated with release layer 17. Layer 20 is subjectedto a subsequent processing step as shown in FIG. 1D, in which thecompressed portions 24 of film 20 are removed thereby exposing substrate18. This removal may be through any appropriate process such as reactiveion etching, wet chemical etching. This forms dams 26 having recesses 28on the surface of substrate 18. Recesses 28 form relief features thatconform generally to the shape of features 16 and mold 10.

[0045] The mold 10 is patterned with features 16 comprising pillars,holes and trenches with a minimum lateral feature size of 25 nm, usingelectron beam lithography, reactive ion etching (RIE) and otherappropriate methods. The typical depth of feature 16 is from 5 nm to 200nm (either including the dimensions of the release layer 17 or excludingthose molecular dimensions), depending upon the desired lateraldimension. In general, the mold should be selected to be hard relativeto the softened thin film, and can be made of metals, dielectrics,polymers, or semiconductors or ceramics or their combination. In oneexperiment, the mold 10 consists of a layer 14 and features 16 ofsilicon dioxide on a silicon substrate 12.

[0046] Thin film layer 20 may comprise a thermoplastic polymer or otherthermoplastic, hardenable, or curable material which may pass from aflowable state to a non-flowing state upon a change in conditions (e.g.,temperature, polymerization, curing or irradiation). During thecompressive molding step shown in FIG. 1B, thin film 20 may be heated ata temperature to allow sufficient softening of the film relative to themold. For example, above the glass transition temperature the polymerhas a low viscosity and can flow, thereby conforming to the features 16without forming a strong adherence to the surface because of thepresence of the release layer 17. The film layer may comprise anythingfrom continuous films of materials, to lightly sintered materials, toloose powders held in place by gravity until the compressive andadherent steps of the molding or microreplication processes. Forexample, the material could be a polymer film, latex film, viscouspolymer coating, composite coating, fusible powder coating, blend ofadherent and powder, lightly sintered powder, and the like. The polymermay comprise any moldable polymer, including, but not limited to(meth)acrylates (which includes acrylates and methacrylates),polycarbonates, polyvinyl resins, polyamides, polyimides, polyurethanes,polysiloxanes, polyesters (e.g., polyethyleneterephthalate,polyethylenenaphthalate), polyethers, and the like. Materials such assilica, alumina, zirconia, chromia, titania, and other metal oxides (orhalides) or semimetal oxides (or halides) whether in dry form or solform (aqueous, inorganic solvent or organic solvent) may be used as themoldable material. Composites, mixing both polymeric materials andnon-polymeric materials, including microfibers and particulates, mayalso be used as the molding material.

[0047] In one experiment, the thin film 20 was a PMMA spun on a siliconwafer 18. The thickness of the PMMA was chosen from 50 nm to 250 nm.PMMA was chosen for several reasons. First, even though PMMA does notadhere well to the SiO₂ mold due to its hydrophilic surface, itsadherence can be reduced further by the use of the release layers of thepresent invention. Good mold release properties are essential forfabricating nanoscale features. Second, shrinkage of PMMA is less than0.5% for large changes of temperature and pressure. See I. Rubin,Injection Molding, (Wiley, N.Y.) 1992. In a molding process, both themold 10 and PMMA 20 were first heated to a temperature of 200° C. whichis higher than the glass transition temperature of PMMA, 105° C. See M.Harmening, W. Bacher, P. Bley, A. El-Kholi, H. Kalb, B. Kowanz, W. Menz,A. Michel, and J. Mohr, Proceedings IEEE Micro Electro MechanicalSystems, 202 (1992). Then the mold 10 and features 16 were compressedagainst the thin film 20 and held there until the temperature droppedbelow the PMMA's glass transition temperature. Various pressures havebeen tested. It was found that the one preferred pressure is about400-1900 psi., especially 500-100 psi. At that pressure, the pattern ofthe features 16 can be fully transferred into the PMMA, particularlywhen the release was expedited by the presence of the release layer 17.After removing mold 10, the PMMA in the compressed area was removedusing an oxygen plasma, exposing the underlying silicon substrate andreplicating the patterns of the mold over the entire thickness of thePMMA. The molding pressure is, of course, dependent upon the specificpolymer being used and can therefore vary widely from material tomaterial.

[0048]FIG. 2 in copending application Ser. No. 08/558,809 shows ascanning electron micrograph of a top view of 25 nm diameter holes witha 120 nm period formed into a PMMA film in accordance with FIG. 1C. Moldfeatures as large as tens of microns on the same mold as the nanoscalemold features have been imprinted.

[0049]FIG. 3 copending application Ser. No. 08/558,809 shows a scanningelectron micrograph of a top view of 100 nm wide trenches with a 200 nmperiod formed in PMMA in accordance with FIG. 1C.

[0050]FIG. 4 in copending application Ser. No. 08/558,809 is a scanningelectron micrograph of a perspective view of trenches made in the PMMAusing the present invention with embodiment that top portions 24 a offilm 20 contact depressed surfaces 16 a of mold 10. The strips are 70 nmwide, 200 nm tall, therefore a high aspect ratio. The surface of thesePMMA features is extremely smooth and the roughness is less than 3 nm.The corners of the strips are nearly a perfect 90 degrees. Suchsmoothness, such sharp right angles, and such high aspect ratio at the70 nm features size cannot be obtained with the prior art.

[0051] Furthermore, scanning electron microscopy of the PMMA patternsand the mold showed that the lateral feature size and the smoothness tothe sidewalls of PMMA patterns fabricated using the present inventionconform with the mold. From our observations, it is clear that thefeature size achieved so far with the present invention is limited byour mold size. From the texture of the imprinted PMMA, it appears that10 nm features can be fabrication with the present invention.

[0052] After the steps 1A-1D, the patterns in film 20 can be replicatedin a material that is added on substrate 18 or can replicated directlyinto substrate 18. FIGS. 5A and 5B show one example of the subsequentsteps which follow the steps of FIGS. 1A-1D. Following formation of therecesses 28 shown in FIG. 1D, a layer of material 30 is deposited oversubstrate 18 as shown in FIG. 5A. Material 30 is deposited through anydesired technique over dams 26 and into recesses 28 between dams 26.Material 30 may comprise, for example, electrical conductors orsemiconductors or dielectrics of the type used to fabricate integratedcircuits, or it comprise ferromagnetic materials for magnetic devices.Next, a lift off process is performed in which a selective chemical etchis applied which removes dams 26 causing material 30 deposited on top ofdams 26 to be removed. FIG. 5B shows the structure which resultsfollowing the lift off process. A plurality of elements 32 formed ofmaterial 30 are left on the surface of substrate 18. Elements 32 are ofthe type used to form miniaturized devices such as integrated circuits.Subsequent processing steps similar to those shown in steps 1A-1D may berepeated to form additional layers on substrate 18.

[0053] FIG. 6 of copending application Ser. No. 08/558,809 is a scanningelectron micrograph of the substrate of FIG. 2 following deposition of 5nm of titanium and 15 nm of gold and a lift off process. In the lift-offprocess, the wafers were soaked in acetone to dissolve the PMMA andtherefore lift-off metals which were on the PMMA. The metal dots have a25 nm diameter that is the same as that of the holes created in the PMMAusing the present invention.

[0054] FIG. 7 of copending application Ser. No. 08/558,809 is a scanningelectron micrograph of the substrate of FIG. 3 following deposition of 5nm of titanium and 15 nm of gold and a lift off process. The metallinewidth is 100 nm that is the same as the width of the PMMA trenchesshown in FIG. 3. FIGS. 6 and 7 have demonstrated that, during the oxygenRIE process in the present invention, the compressed PMMA area wascompletely removed and the lateral size of the PMMA features has notbeen changed significantly.

[0055]FIG. 8 is a cross sectional view of substrate 18 of FIG. 1Dfollowing an example alternative processing step that replicates thepatterns in film 20 directly into substrate 18. In FIG. 8, substrate 18has been exposed to an etching process such as reactive ion etching,chemical etching, etc., such that recesses 40 are formed in substrate18. These recesses 40 may be used for subsequent processing steps. Forexample, recesses 40 may be filled with material for use in fabricatinga device. This is just one example of a subsequent processing step whichcan be used in conjunction with the present invention.

[0056] Molding processes typically use two plates to form malleablematerial therebetween. In the present invention, substrate 18 and body12 (mold 10) act as plates for the imprint process of the invention.Substrate 18 and body 12 should be sufficiently stiff to reduce bendingwhile forming the imprint. Such bending leads to deformation in thepattern formed in the film 20.

[0057]FIG. 9 is a simplified block diagram of apparatus 50 forperforming nanoimprint lithography in accordance with the invention.Apparatus 50 includes stationary block 52 carrying substrate 18 andmoveable molding block 54 carrying mold 10. Blocks 52 and 54 carry thesubstrate 18 and mold 10 depicted in FIGS. 1A-1D. A controller 56couples to x-y positioner 58 and z positioner 60. An alignment mark 64is on mold 10 and complimentary mark 68 is on substrate 18. Sensor 62carried in block 54 couples to alignment marks 64 and 68 and provide analignment signal to controller 56. Controller 56 is also provided withinput output circuitry 66.

[0058] In operation, controller 56 controls the imprinting of mold 10into film 20 on substrate 18 by actuating z positioner 60 which movesblock 54 in the z direction relative to block 52. During the imprintingprocess, precise alignment of mold 10 and film 20 is crucial. This isachieved using optical or electrical alignment techniques. For example,sensor 62 and alignment marks 64 and 68 may be an optical detector andoptical alignment marks which generate a moiré alignment pattern suchthat moiré alignment techniques may be employed to position mold 10relative to film 20. Such techniques are described by Nomura et al. AMOIRÉ ALIGNMENT TECHNIQUE FOR MIX AND MATCH LITHOGRAPHIC SYSTEM, J. Vac.Sci. Technol. B6(1), Jan/Feb 1988, pg. 394 and by Hara et al., ANALIGNMENT TECHNIQUE USING DEFRACTED MOIRÉ SIGNALS J. Vac. Sci, Technol.B7(6), Nov/Dec 1989, pg. 1977. Controller 56 processes this alignmentinformation and adjusts the position of block 54 in the x-y planerelative to film 20 using x-y positioner 58. In another embodiment,alignment marks 64 and 68 comprise plates of a capacitor such thatsensor 62 detects capacitance between marks 64 and 68. Using thistechnique, alignment is achieved by moving block 54 in the x-y plane tomaximize the capacitance between alignment marks 64 and 68. Duringimprinting, controller 56 may also monitor and control the temperatureof film 20.

[0059] It should be understood that the invention is not limited to thespecific technique described herein, and may be implemented in anyappropriate lithographic process. Generally, the mold should be hardrelative to the film during the molding process. This may be achievedfor example, by sufficiently heating the film. Additionally, it shouldbe understood that the invention is not limited to the particular filmdescribed herein. For example, other types of films may be used. In onealternative embodiment, a thin film may be developed which has achemical composition which changes under pressure. Thus, following theimprint process, a chemical etch could be applied to the film whichselectively etches those portions whose composition had changed due toapplied pressure. In anther embodiment, after molding of the thin filmto create a thickness contrast in the thin film, a material is depositedon the thin film and the thickness contrast then is transferred into thesubstrate.

[0060] Although the present invention has been described with referenceto preferred embodiments, workers skilled in the art will recognize thatchanges may be made in form and detail without departing from the spiritand scope of the invention.

EXAMPLES

[0061] An example of a lithographic process according to the presentinvention forming a pattern in a film carried on a substrate would bepracticed by the steps of depositing a film on a substrate to provide amold having a protruding feature and a recess formed thereby, thefeature and the recess having a shape forming a mold pattern. At least aportion of the surface, (in this case a surface of silica orsilicon-nitride is preferred) such as the protruding feature(s), if notthe entire surface (the protrusions and valleys between the protrusions)onto which the film is deposited, is coated with the release materialcomprises a material having the formula:

RELEASE-M(X)_(n-1)-, Formula I

RELEASE-M(X)_(n-m-1)Q_(m) Formula II

or

RELEASE-M(OR)_(n-1)-, Formula III wherein

[0062] RELEASE is a molecular chain of from 4 to 20 atoms in length,preferably from 6 to 16 atoms in length, which molecule has either polaror non-polar properties;

[0063] M is a metal or semimetal atom;

[0064] X is halogen or cyano, especially Cl, F, or Br;

[0065] Q is a hydrogen or alkyl group,

[0066] m is the number of Q groups,

[0067] R is hydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1to 4 carbon atoms; and;

[0068] n-m-1 in Formula II is at least 1 (m is 2 or less), preferably 2(m is 1 or less), and most preferably at least 3 (m is 0)

[0069] n is the valence −1 of M.

[0070] In particular, silicon compounds (pure or in solution) of C1 toC4 alkyl (for R), wherein X is F, and RELEASE is perfluorinated alkylare preferred. Particularly 1H, 1H, 2H,2H-perfluorododecyltrichlorosilane (commercially available as a 97%solids solution) has been found to be particularly useful in thepractice of the invention. (The triethoxysilane counterpart tends torequire a more active stimulus to assure extensive bonding to thesurface. The 1H, 1H, 2H, 2H-perfluorododecylmethyldichlorosilane, wouldclose in effectiveness to the 1H, 1H, 2H,2H-perfluorododecyltrichlorosilane, with the slightly reduced activityof the additional methyl group replacing one of the chloro groups on thesilane. Similarly, the commercially available 1H, 1H, 2H,2H-perfluorododecyldimethylmonochlorosilane would be slightly lessreactive, yet again). This 1H, 1H, 2H,2H-perfluorododecyltrichlorosilane compound is coated (in a roomtemperature, air tight, ventilated environment) at about 0.01mg/m² ofsurface area, heated (to about 40 to 50 degrees Centigrade) to react thematerial to the surface, and cooled. This forms a coating on the surfacein which the reactive portion of the molecule (the SiF bonds) reactswith the silica or silica nitride surface, forming a coating comprisingthe silicon atom bonded to the surface with a tail of theperfluorinatedalkyl group extending from the surface to leave a reducedfriction surface. The mold is then urged into the film whereby thethickness of the film under the protruding feature is reduced and a thinregion is formed in the film. The mold is removed from the film,processing the relief. The thin region is removed, exposing a portion ofthe surface of the substrate which underlies the thin region. Theexposed portion of the surface of the substrate substantially replicatesthe mold pattern. The improvement of having at least a portion of saidprotruding feature and a portion of said release having the releasematerials of the invention bonded thereto improves the release and theresolution of the mold operation. Importantly, the release coating ofthe invention has been proven to be persistent and reusable,particularly where modest pressures (e.g., less than 1000 psi are used,and where the film does not contain ingredients which chemically attackthe release coating. The selection of the release coating withperfluorinated R groups assists in providing chemical attack resistantcoatings. It is important to note that the processes and release coatedmaterials of the present invention can be made by the simple coating andreaction of the release coating forming materials of the presentinvention, and that these materials, and the broad range of equivalentsare broadly enabled. The materials may be coated as pure material andallowed to react at ambient conditions (where the materials areparticularly active to the surface), they may be in solution to dilutethe coating (taking care to select solvents which are themselves notactive to the release-coating forming compounds and preferably not tothe surface), their reaction may be accelerated by heat, catalysts,initiators (either thermal, or photoinitiators, for example, such asfluorinated sulfonic acids, sulfonium or iodonium photoinitiators withcomplex halide anions, such as triarylsulfonium hexafluoroantimonate,diaryl iodonium tetrafluoroborate), accelerators and the like.

[0071] The release-forming coatings of the present invention may beapplied as release coatings by simply applying the chemical compounds toa surface to which they react (essentially any surface with freeHydrogen atoms, which react with halogens, organic acids, silicic orinorganic acids, hydroxyl groups, hydrogen-containing amine groups,mercaptan groups, and the like). The surfaces may be polymeric surfaces,metallic surfaces, alloy surfaces, ceramic surfaces, composite surfaces,organic surfaces, inorganic surfaces, smooth surfaces, rough surfaces,textured surfaces, patterned surfaces, and the like. The use oftemperatures and solvents is limited solely by their effect on thesubstrate and the coating. That is temperatures should not be usedduring the application of the surface which would degrade the surface orthe coating material or so rapidly volatilize the coating material thatit would not adhere. As noted elsewhere, catalysts and initiators may beused, but the preferred release coating forming compounds of theinvention generally can react at room temperature without anysignificant stimulus being applied.

[0072] The 1H, 1H, 2H, 2H-perfluorododecyltrichlorosilane has beenapplied as a release surface to Si surfaces, SiN surfaces and the likesolely by application of the commercially available 1H, 1H, 2H,2H-perfluorododecyltrichlorosilane (without modification) to the surfaceat room temperature. The comppounds of Formula I are the most preferred(primarily because of their activity), the compounds of Formula II lesspreferred, and the compounds of Formula III least preferred because oftheir reduced reactivity to surfaces.

What is claimed is:
 1. A lithographic method for forming a pattern in afilm carried on a substrate, comprising the steps of: depositing a filmon a substrate to provide a mold having a protruding feature and arecess formed thereby, the feature and the recess having a shape forminga mold pattern; urging the mold into the film whereby the thickness ofthe film under the protruding feature is reduced and a thin region isformed in the film; removing the mold from the film; processing therelief whereby the thin region is removed exposing a portion of thesurface of the substrate which underlies the thin region; and wherebythe exposed portion of the surface of the substrate substantiallyreplicates the mold pattern, the improvement comprising at least aportion of said protruding feature and a portion of said release havebonded thereto a release material comprising an inorganic linking groupbonded to a molecular chain having release properties.
 2. The method ofclaim 1 wherein said release material comprises a material having theformula: RELEASE-M(X)_(n-1)- or RELEASE-M(OR)_(n-1)-, wherein RELEASE isa molecular chain of from 4 to 20 atoms in length, preferably from 6 to16 atoms in length, which molecule has either polar or non-polarproperties; M is a metal or semimetal atom; X is halogen or cyano,especially Cl, F, or Br; R is hydrogen, alkyl or phenyl, preferablyhydrogen or alkyl of 1 to 4 carbon atoms; and; (n) is the valence −1 ofM.
 3. The process of claim 2 wherein RELEASE comprises a highlyfluorinated organic group.
 4. The process of claim 3 wherein said highlyfluorinated group comprises a perfluorinated alkyl group.
 5. The processof claim 2 wherein M is Si.
 6. The process of claim 2 wherein X ishalogen.
 7. The process of claim 2 wherein X is chloro or bromo.
 8. Theprocess of claim 6 wherein M is Si.
 9. The process of claim 7 wherein Mis Si.
 10. A process for improving the release properties of a surfacecomprising: a) providing a surface; b) contacting that surface with arelease forming material wherein said release forming material comprisesa material having the formula: RELEASE-M(X)_(n-1) orRELEASE-M(OR)_(n-1)-, wherein RELEASE is a molecular chain of from 4 to20 atoms in length, preferably from 6 to 16 atoms in length, whichmolecule has either polar or non-polar properties; M is a metal orsemimetal atom; X is halogen or cyano, especially Cl, F, or Br; R ishydrogen, alkyl or phenyl, preferably hydrogen or alkyl of 1 to 4 carbonatoms; and; (n) is the valence −1 of M.
 11. The process of claim 10wherein said release forming material comprises a material of theformula: RELEASE-M(X)_(n-1)- wherein RELEASE is a molecular chain offrom 4 to 20 atoms in length, which molecular chain has either polar ornon-polar properties; M is a metal or semimetal atom; X is halogen orcyano, especially Cl, F, or Br; and (n) is the valence −1 of M.
 12. Theprocess of claim 11 wherein RELEASE comprises a highly fluorinatedorganic group.
 13. The process of claim 12 wherein said highlyfluorinated group comprises a perfluorinated organic group.
 14. Theprocess of claim 11 wherein said highly fluorinated group comprises aperfluorinated alkyl group of from 4 to 16 carbon atoms.
 15. The processof claim 11 wherein M is Si.
 16. The process of claim 12 wherein M isSi.
 17. The process of claim 13 wherein M is Si.
 18. The process ofclaim 14 wherein M is Si.
 19. A surface having good antiadherentproperties comprising a surface having bonded thereto the residue ofmaterial of the formula: RELEASE-M(X)_(n-1)- or RELEASE-M(OR)_(n-1)-,wherein RELEASE is a molecular chain of from 4 to 20 atoms in length,preferably from 6 to 16 atoms in length, which molecule has either polaror non-polar properties; M is a metal or semimetal atom; X is halogen orcyano, especially Cl, F, or Br; R is hydrogen, alkyl or phenyl,preferably hydrogen or alkyl of 1 to 4 carbon atoms; and; (n) is thevalence −1 of M, said material being bonded to said surface only througha bond directly to M where a group X or OR has been removed to enablebonding to said surface, with the group RELEASE still attached to M. 20.The surface of claim 19 wherein said material comprises a material ofthe formula: RELEASE-M(X)_(n-1)- wherein RELEASE is a molecular chain offrom 4 to 20 atoms in length, preferably from 6 to 16 atoms in length,which molecule has either polar or non-polar properties; M is a metal orsemimetal atom; X is halogen or cyano, especially Cl, F, or Br; and (n)is the valence −1 of M.
 21. The surface of claim 20 wherein RELEASEcomprises a highly fluorinated group.
 22. The surface of claim 21wherein said highly fluorinated group comprises a perfluorinated group.23. The surface of claim 22 wherein said highly fluorinated groupcomprises a perfluorinated group of from 4 to 16 carbon atoms.
 24. Thesurface of claim 20 wherein M is Si.
 25. The surface of claim 21 whereinM is Si.
 26. The surface of claim 22 wherein M is Si.
 27. The surface ofclaim 23 wherein M is Si.
 28. A surface having good antiadherentproperties comprising a surface having bonded thereto the material ofthe formula: RELEASE-M(X)_(p-2) or RELEASE-M(OR)_(p-2), wherein RELEASEis a molecular chain of from 4 to 20 atoms in length, preferably from 6to 16 atoms in length, which molecule has either polar or non-polarproperties; M is a metal or semimetal atom; X is halogen or cyano,especially Cl, F, or Br; R is hydrogen, alkyl or phenyl, preferablyhydrogen or alkyl of 1 to 4 carbon atoms; and; p is the valence of M,said material being bonded to said surface only through a bond directlyto M. 29 The surface of claim 19 wherein the surface comprises apatterned mold surface.
 30. The method of claim 1 including heating thethin film to a temperature to allow sufficient softening of the filmrelative to the mold prior to the step of urging.
 31. The method ofclaim 1 wherein the feature on the mold is formed from material selectedfrom the group consisting of: semiconductors, dielectrics, metals,ceramics, polymers and their combination.
 32. The surface of claim 19wherein said surface comprises a material selected from the groupconsisting of: semiconductors, dielectrics, metals, ceramics, polymersand their combination.
 33. The method of claim 1 wherein the step ofprocessing comprises reactive ion etching.
 34. The method of claim 1including repeating the steps of obtaining a mold, urging, removing, andprocessing to form a multilayered device.
 35. The method of claim 9wherein the material is selected from the group consisting ofsemiconductors, dielectrics, metals, ceramics, polymers, and theircombination.
 36. A lithographic method for forming a pattern in a filmcarried on a substrate, comprising the steps of: obtaining a substratehaving a release coating thereon formed by the reaction of a compound ofthe formula RELEASE-M(X)_(n-1)- or RELEASE-M(OR)_(n-1)-, wherein RELEASEis a molecular chain of from 4 to 20 atoms in length, preferably from 6to 16 atoms in length, which molecule has either polar or non-polarproperties; M is a metal or semimetal atom; X is halogen or cyano,especially Cl, F, or Br; R is hydrogen, alkyl or phenyl, preferablyhydrogen or alkyl of 1 to 4 carbon atoms; and; (n) is the valence −1 ofM, depositing a film on the substrate; obtaining a mold having aprotruding feature and a recess formed thereby, the feature and therecess having a shape forming a mold pattern; urging the mold into thefilm creating a thickness contrast pattern in the film; removing themold from the film; and transferring the thickness contrast pattern inthe film onto the substrate.
 37. A process for improving the releaseproperties of a surface comprising: a) providing a surface; b)contacting that surface with a release forming material wherein saidrelease forming material comprises a material having the formula:RELEASE-M(X)_(n-m-1)Q_(m), RELEASE is a molecular chain of from 4 to 20atoms in length, preferably from to 16 atoms in length, which moleculehas either polar or non-polar properties; M is a metal or semimetalatom; X is halogen or cyano, especially Cl, F, or Br; Q is a hydrogen oralkyl group, m is the number of Q groups, n-m-1 is at least 1, and n isthe valence −1 of M.
 38. The process of claim 2 wherein said releasematerial comprises a material having the formula: RELEASE-M(X)_(n-1)-.39. The surface of claim 28 wherein said release material comprises amaterial having the formula: RELEASE-M(X)_(n-1)-.
 40. The process ofclaim 38 wherein M is Si; X is halogen Cl or Br; RELEASE isperfluoroalkyl of 6 to 20 carbon atoms; and n is
 3. 41. The surface ofclaim 39 wherein M is Si; X is halogen Cl or Br; RELEASE isperfluoroalkyl of 6 to 20 carbon atoms and n is 3.